Process of extracting titanium compounds from titaniferous material and the product obtained thereby



G. JEBSEN. PROCESS OF EXTRACTING TITANIUM COMPUNDS FROM TITANIFEROUS MAT RIAL AND THE PRODUCT OBTAINED THEREBY. APPLlcATmN FILED ocT. 12. 19x?.

Attorneys.

UNITED STATES PATENT OFFICE.

GUSTAV JEBSEN, 'OF CHRISTIANIA, NORWAY, ASSIGNOR,

BY MESN'E ASSIGNMENTS, 'ro

TITAN CO. A /S., 0F GHRISTIANIA, NORWAY.

PROCESS 0F EXTBACTING TITANIUM COMPOUNDS FROM TITANIFEROUS MATERIAL AND THE PRODUCT OBTAINED THEREBY.

Specification of Letters Patent.

Application filed October 12, 1917. A Serial No. 196,977.

To all whom it may concern Be it known that I, GUs'rAv JnsEN, a subject of Norway, and a resident of Christiania, Kingdom of Norway, have invented certain, new and useful Improvements in Processes of Extracting Tltanium Compoundsrfrom Titaniferous Material and the Product Obtained Thereby, of which the following is a specification.

This invention relates to a process for the recovery from titaniferous materials, such as ilmenite, of titanium in the form of hydrates and as a precipitate. The process broadl contemplates the decomposing of the titani erous material, lixiviatin the resultant product and recipitating tle hydrates from the solution thus obtained. In case a titaniferous material containing iron is made use of and the precipitate is desired to be comparatively free from iron, the process contemplates avoidance of the undesired iron in any suitable manner, all as hereinafterV set forth in detail.

I have discovered that when my process is employed a less quantity of decomposing agent may be used than would be required to form normal salts with the base-forming material present in the solution obtained by the lixiviation.

In carrying out the decomposition stage of the process I have evolved a novel method yby the use of apparatus found to be partielllarly advantageous for this purpose, and the same is presented herewith as the preferred method of conductin this operation.

Furthermore the so ution which is formed in the carrying out of my process is novel in itself and possesses certain advantageous qualities not heretofore known or understood.

In the precipitation stage of the process I prefer to follow the method which is the discovery of Morten Fladmark and which is embodied in United States Letters Patent No. 1,288,863 granted December 24th, `1918, and while 'in order that my complete process may be understood that method of precipitation is herein described, no specific claims are presented directed solely to this feature. By way of introduction on this -point I may sav that precipitation of the hydrates may be eii'ected from my solution, which is preferably very concentrated, by the application of heat and without dilution.

The treatment of ilmenite and other materials containing iron and titanium for the purpose of obtainin titanium hydrates has hitherto been carrie out in various manners and various processes have been proposed for this purpose. Accordin to known methods the materials have posed or 'rendered soluble by fusion with potassium or sodium carbonates, bisulfates or other known dissolving agents. The decomposition or dissolution has also been effected by means of acids such as sulfuric acid, hydrochloric acid, etc. According to these known methods the dissolution has been effected by the use of such a large quantity of the dissolving Aagent that a practically complete dissolution of the titaniferous material in question has been obtained in one single operation. To obtain this an excess of dissolvingor'decomposing agent has been employediildthis excess quantity then represents a direct loss of dissolving agent or increased expenses in connection with the recovery of such excess quantity.

When these well known processes are employed, and a solution of titanium compounds is subsequently obtained by dissolving the decomposition product in water, it has been found that the excess of decomposition'agent present, even thou h slight, will prevent an economical precipltation of the hydrates by heatin unless the solution is first diluted. The dilution of this solution results in inconvenience and expense in handling and precipitating therefrom. Furthermore, when a amount-of water is added to the decomposition product, unless there vis an excess of decomposition 'agent present, the titanium compounds first dissolved undergo partial hydrolysis, and this hydrolysis increases with the amount of water employed.

In addition to the above, when a dilute solution is employed the filtrate resulting after the precipitation of the hydrate will be of such low concentration that the recovery of the unhydrolyaedsalts of the metals present in the original material and of the een decomf comparatively large convenient means decomposn agent liberated by the hydrolysis can be e ected only at large expense.

Now, according to the present mvenltion, practically complete decomposition of the titaniferous material may be effected by the use of a considerably smaller quantity of decomposing agent than has heretofore been considered as theoretically possible: and, as stated above, a highly concentrated solution may be prepared from the resultant deoonr ition product from which Without dilution a satisfactor yield of comparatively pure titanium hy rates can be recipitated.

As ilmenite is the most avai able titaniferous material found in nature, that ore will be used in the following illustration of the manner in which the process is carried out, sulfuric acid Will be spoken of as the decomposition agent, and the apparatus herein shown Will be employed in the decomposition step of the process: but it is to be understood that the choosing of ilmenite and the sulfuric acid, and the employment of the said apparatus are for the purpose of illustration only and are not 'to be taken as limitations on the invention.

In these drawings `Figure 1 is a side elevation of an endless conveyer sup lied with an oven for la portion of its lengt the side Walls of the oven not being illustrated, and the roof and ends of the oven being in vertical section; and Fi 2 is a cross-section on the line II II of Fig, 1 with the side Walls of the oven added but with the carrier or propeller Wheel omitted, the omission of the aforesaid parts in the two figures being for clearness of illustration.

Taking up now the specific example chosen for illustrative purposes, the ilmenite rst having been reduced to convenient form for decomposition, for instance, first having been pulverized, is placed in a suitable mixer and t ioroughly mixed with the desired quantity of sulfuric acid. I have found that sulfuric acid containing 94 per cent. H250, in the proportion by Weight of one to one will give favorable results. When the ilmenite composition is then all owed to take place and sulfuric acid have been thoroughly mixed, they take the form of a slime. Deand if desired may be accelerated by the aplication of heat. To accomplish this result I have found, however, that continued application of lthe heat is not necessary for when the temperature of the mixture is raised to 100 C. or thereabout, the desired decomposition will take place with speed and violence. When the reaction is completed the mass will have formed into a more or less solid cake.

The apparatus herein illustrated forms a for carrying on this decom osition.

T e apparatus comprises an endless :on-

veyer composed of a series of buckets 3, 3 attached to and carried by the links 4, 4 of the conveyer. The adjacent pairs of links are joined at their respective ends by means of cross-rods 5, 5 upon which are rotatably mounted pairs of flanged 6, 6 which latter run on pairs of rails 8, 8 suitably mounted along the upper and lower travel of the conveyer to support the same. At both ends of the conveyer are located pairs of suitably mounted sprocket wheels 10, 10 which serve to drive and support the conveyer in the usual manner. This type of conveyer is Well known in the conveyer art and no specific drivingmeans are illustrated.

Each of the buckets is provided With a transverse lip, illustrated at 12, at one of its ends, which overlaps the end wall of the adjacent bucket so that a continuous stream of the aforesaid slime ma be supplied to the buckets Without loss tween them. The means of supplying the slime are indicated by the valved inlet pipe 14 mounted at one end of the conveyer in a osition to discharge into the buckets t ereof. A discharge-hopper 15 is mounted at the other end of the conveyer, into which the decomposed contents of each bucket will fall by gravity as the buckets are turned over in *traveling around the sprocket Wheels adjacent thereto. The hopper is intended to discharge the decomposed mass into the apparatus to be next employed as will readily be understood.

As here illustrated, the charging end of the conveyer is located in an oven 17, access to which may be had through the doors 18, 18. A series of steampipes Q0, 2() equipped With radiating fins and supplied with steam from steampipe 22 is located beneath the upper tier of buckets and serves to supply heat to the contents thereof. A similar series of radiating steampipes 23, 23 supplied with steam from steainpipe 25 may be located beneath the overturned buckets on their lower travel for the purpose of drying and preliminarily heating them. Each series of radiating steampipes is illustrated as being supported on rollers 27, 27 to allow for ex ansion and contraction of the pipes.

In t e arrangement illustrated the supply of slime Will be so regulated that each bucket is properly filled; and the rate of travel and length of conveyer will be such that the desired decomposition will have taken place just prior to the dumping of the bucket contents, then a more or less solid cake. into the hopper 15.

The solution from which `the hydrates are `to be precipitated is made from this cake,

and to this end, the cake is first crushed by the employment of ang7 suitable crusher. With this in view the size and sha e of the buckets 3 3 should be such that t e cakes traction Wheels,4

formed therein may be fed from the hopper 15 directly to the crusher. The mass having been crushed is then lixiviated preferably with a series of vessels according to the counter-current principle, cold Water being employed in such quantity that crystallization is just avoided in the last vessel of the series. As the counter-current method of lixiviation is well known" in other arts a complete de scription thereof is here omitted, attention being called to the fact that by its employment, the decomposition product is l1xivi ated with a solution of the said product itself. i The result of this lixiviation is to form a concentrated solutionl of the soluble substances in the decomposition product, which solution contains less sulfuric acid than would be required to form normal salts with the basefforming material present therein.

In the last vessel of the series will also be found a residue which may be called residue No. 1. In carrying out the decomposition by steps this residue is treated in the saine manner as the original ilmenite and the process repeated up to and including the lixiviation. Thereby a second solution is formed, of a like character as the first solution, and a residue No. 2. This residue may be given the same treatment as residue N o. 1 and 'a third solution and a residue N o. 3 obtained. In most instances this latter residue Awill consist principally of silicio acid com` pounds of the ore. In cases where residue No. 3 still contains some undissolved titanium, the above operation ma be repeated and so ou step by step until t e titanium is entirely dissolved.

It is not necessary for the successful carrying out of my rocess to attain a complete decomposition of) the ilmenite, the point at which it is desirable to carry the decomposition being largely ldetermined by economic reasons and comparative costs. Thus if desired the decomposition may be terminated at the end of the first, second or third, etc., ste s.

s an example of the eliciency of this portion of my process when carried on by steps, the following data and calculations are presented. Experiments were carried on with ilmenite containing the following materials which could be rendered soluble by treatment with sulfuric acid:

mal sulfates one part by weight of the l ilmenite would require 1.9 parts by weight sought, this result may be obtained by reducing the iron present in the solution from a ferr-1c to a ferrous condition. This reduction is preferably carried on at this point and may be accomplished in any well known and suitable manner. The desired purity of product may also be attained without reduction of the iron by a subsequent treatment of the precipitate, later to be described.

It is immaterial so far as the precipitation is concerned Whether the solution to be submitted to ,precipitation is one in which the iron has been reduced, or the one obtained directly by lixiviation. The solution in either case may now be submitted to precipitation by means of any well known suitable method. I prefer, however, to effect precipitation by the application of heat, without diluting the sol'ution. To this end the solution is placed in a lead-lined container equipped with coils of lead pipe. Heat is applied by passing steam through the'coils, and precipitation takes place. It has been found that the precipitation may be satisfactorily brought about by heating the solution to approximately 800 C., and continuing the application of heat for several hours. Where it is desired to increase the rapidity of precipitation, the temperature of the solution may be raised even above the boiling point by the employment of suitable apparatus for this purpose.

Considering that the above process has been carried on without the reduction of the iron, the preci itate thrown down for many purposes may e considered the linal product herein sought. It is rich in titanium hydrates and contains less iron than the precipitates which have been obtained in accordance with previous processes from dilute solutions and without the iron.reduc tion.

However, for some purposes, ,particularly for use in the formation of certain pigments where the presence of small quantities of iron is objectionable, the process should include the reduction of the iron as above outlined or the precipitate should be treated to eliminate the objectionable iron. A suitable treatment of the precipitate for this purpose is to subject it tothe entire process above outlined, starting the ilmenite and omitting the reduction of the iron. Thetitanium hydrate thus resprecipitated will be found to be comparatively .free from iron and suitable for use in the formation of pigments.

The undecomposed salts Aand Vthe decomposing agent liberated by the hydrolysis of the titanium compounds obviously can, onl

account of their comparatively high conceiiff normal salts with the base-forming material tration, be recovered from theltrate much more readily than in the case of the previous processes in which precipitation was brought about from a dilute solution.

The word hydrates as used herein isemployed as drated oxids with or without more or less basic salts or adsorbed acids.

The foregoing detailed description has been given for clearness of understanding and no undue limitation should be deduced therefrom, but the ap ended claims should be construed as broa ly as 'permissible in view of the prior art.

What claim as new and desire to secure by Letters Patent of the United States is:

1. The process of effecting the decomposition of titaniferous materials, which comprises treating the material with a decomposing agent and subjecting the resultant batch to heat by means of an endless conveyer, the fbuckets of which are passed through a heated area, whereby the decomposed material is formed into a comparatively solid mass.

2. The process of effecting the decomposition of titaniferous material, which comprises treatin the material with sulfuric acid and subjecting the resultant batch to initial heat by means of an endless conveyer, the buckets of which are passed through a heated area, whereby the decomposedl material is formed into a comparatively solid mass.

3. The process of preparing from titaniferous. materials a lsolution containing a titanium compound, which comprises subjecting the material to decomposition by treating the material with a decomposing agent and lixiviating the resultant product, the quantity of decomposing agent emplo ed being less than would be required to gorm normal salts with the base-forming materials present in the resultant solution.

4. The process of preparing from titaniferous materials containing iron a solution principally of titanium and iron compounds, which comprises subjecting the material to decomposition, by treating the material with a decomposing agent and lixiviating the resultant product, the quantit of decomposing agent employed being ess than is-required to form normal salts with the basea general term and includes hy ant product, the quantity of sulfuric acid g from annui solution employed being less than is required to form present in the resultant solution.'

6. The process of preparing from titanifcrous materials containing iron a solution principally'of titanium and iron compounds, which comprises subjecting the material to decom osition by treating the material with sulfuric acid in the proportion by weight of one part sulfuric acid to one part of the material, and lixiviating the resultant product.

7 The process of preparing from titanifcrous materials containing iron a solution principally of titanium and iron compounds, which comprises subjecting the material to decomposition, by treating the material with sulfuric acid, subjecting the material thus treated to an initial heat, and lixiviating the material after heating, the quantity of sulfuric acid employed being less than is required to form normal salts with the baseforming material present in the 'resultant solution.

8. The process of preparing from titanif- .ei-fous materials containing titanium and iron in solid-form a solution of titanium and iron compounds, which comprises subjecting the material to decomposition by treating the material with sulfuric acid to form a slime, subjecting the slime to heat and thereby reducing the slime to a solid mass, and lixiviating the said mass, the quantity of sulfuric acid employed being less than is required to form normal salts with the base-forming material present in the resultant solution. 9. The process of reparing from titaniferous materials a so ution containing a titanium compound, which comprises subjeoting the material to decomposition by treatin agent lixiviating the decomposition product with water to form a solution containing a titanium compound, and treating fresh decomposition product with the solution thus formed. y v

10. The process of preparing from titaniferous materials a concentrated solution containing a t'tanium compound, which comprises subjecting the material to decomposition by treating the material with a decomposing agent, and lixiviatng the resultant roduct with a solution containing a vtitanlum compound obtained by treating the decomposition product with water, said lixiviation being carried out according to the the material with a decomposing counter-current principle and being continued until a concentrated solution i's obtained.

11. The process ofipreparing from titaniferous materials containing iron a solution principally of titanium and iron compounds, which comprises subjecting the material to decomposition by treating the material with a decomposing agent, lixiviating tlie decomposition product with Water to form a solution containing combined 'titanium and combined iron, and lixiviating fresh decomposition product With the solution thus formed.

12. The process of preparing from titaniferous materials containing iron a concentrated solution pricipally of titanium and iron compounds, which comprises subjecting the material to decomposition by treating the material with a decomposing agent, and lixiviating the resultant product with a solution containin compounds of titanium and iron obtained y treating the decomposition product With Water, said lixiviation being carried out according to the counter-current principle and being continued until a concentrated solution is obtained.

13. The process of preparing from titaniferous materials containing iron a concentrated solution principally of titanium and iron sulfates, which comprises subjecting the material to decomposition by treating the material with sulfuric acid, and lixiviating the resultant product with a solution containing sulfates of iron and titanium obtained by treating the decomposition product with water, said lixiviation being carried out accordingto the counter-current principle and being continued until aconcentrated solution is obtained, which solution contains substantially no more of the SO, radical than would be required to combine With the base-forming material' present to form normal salts.

14. The process of preparing from titaniferous materials containing iron a solution principally of titanium and viron sulfates, which comprises subjecting the material to decom ostion by treating the material with sulfuric acid and subjecting the resultant product to lixiviation with a solution containing sulfates of iron and titanium obtained by treating the decomposition product with water, the said lixiviation being carried out according to the munten-current rinciple and the amount of water employed eing such that a saturated solution is obtained. Y

15. The process of preparing from titaniferous materials a titaniumV hydrate, which comprises subjecting the material to decomposition by treating the material with a decomposing agent, lixiviatin the resultant product and precipitating the ydrates from Aliziiviatinp` the resultant pro the solution thus obtained by the app-lication of heat, the quantity of decomposin agent employed being less than is require to form normal salts with the base-forming material present in the solution.

16. The process of preparing from titaniferous materials containing iron a titanium hydrate comparatively free from iron compounds, Which comprises subjecting the material to decomposition lby treating the material with adecom osing agent, lixiviating the resultant product according to the counter-current princi le with Water in suiicient quantity 4to orm a concentrated solution, and effecting recipitation of the said hydrate from the so ution thus obtained by the application of heat.

17. The process of preparing from tii taniferous materials contalning iron a titanium hydrate, which comprises subjecting the material to decomposition by treating the material with a decomposing a ent, lixiviating the resultant product, eecting preci itation in the solution thus obtained, su jecting the precipitate to the action of the decomposing agent, lixiviating the resultant product, and precipitatin the l precipitating the hydrate from the solution.

19. The process of preparing from titaniferous materials containing iron a titanium hydrate, which comprises subjecting the material to decomposition by treating the material with a decomfposing agent,

uct, reducing the ferrie iron present in the solution to the ferrous condition, and precipitating the hydrate from the solution, the quantity of decomposing agent employed being less than is required to form normal salts with the base-forming material present in the so-y lution.

20. As a new and useful article a solution essentially of combined titanium and containing an` acid radical, the solution being formed from decomposition product obtained by the treatment of titaniferous material'with a decomposing agent containin an acid radical, the acid radical contained in the solution being in less quantity than would be present if all of the baseformin material in the solution were in the form o normal salts.

21. As a new and useful article, a solution essentially of combined titanium and -containing the SO, l"radical, the solution being formed from decomposition product cal, the solution being formed from decomobtamed by the treatment of titaniferous position roduct obtained by the treatment materials with sulfuric acid, the S04 radical of ttani erous materials with sulfuric acid, contained in the solution being in less uanthe SO2 radical eontained in the solution 5 tity than would be present if all of the asebeingr in less quantity than would be present 15 formin material in the solution were in the if all of the base-forming material in the soform o normal Sulfates. lution were in the form of normal sulfates. 22. As a new and useful article2 a solu- Signed at Christiania, Norway, this 14th ti'on essentially `of combined titanium and day of September, 1917.v lo containing combined iron and the SO4 radi- G. JEBSEN.

It is hereby certified Ithat in Letters Patent No. 1,333,819, granted March 16, 1920, upon the application of Gustav Jebsen, of Christiania, Norway, for an improyernent in Processes of Extracting Titanium Compounds from Titaniferous Material and the Product Obtained Thereby, specification requiring correction as follows: Page 6, line 14, claim 22, for S0," read S04; and that the said Letters Patent should be read with this correction therein that the somemay conforxn to the record of the case in the Patent O'fice.

Signed and sealed this 26th day of April, A. D., 1921 T. E. ROBERTSON,

Commissioner of Patente.

an error appears in the printed [smh] 

